JP2007533100A - Battery safety element and battery equipped with the same - Google Patents

Battery safety element and battery equipped with the same Download PDF

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JP2007533100A
JP2007533100A JP2007508274A JP2007508274A JP2007533100A JP 2007533100 A JP2007533100 A JP 2007533100A JP 2007508274 A JP2007508274 A JP 2007508274A JP 2007508274 A JP2007508274 A JP 2007508274A JP 2007533100 A JP2007533100 A JP 2007533100A
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battery
metal plate
pressure
safety element
electrically connected
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JP4642838B2 (en
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チョ、ジョン‐ジュ
チャン、スン‐キュン
ジャン、ミン‐チュル
リー、ジェ‐ヒュン
リー、ジュン‐ホワン
ハ、ソー‐ヒュン
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LG Chem Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50Current conducting connections for cells or batteries
    • H01M50/572Means for preventing undesired use or discharge
    • H01M50/574Devices or arrangements for the interruption of current
    • H01M50/578Devices or arrangements for the interruption of current in response to pressure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

Disclosed is a battery safety device having a first metal plate, a second metal plate, and a pressure-sensitive conducting film interposed between both metal plates and adapted to exhibit electrical conductivity when a predetermined pressure or higher is applied. The first and second metal plates are electrically connected to the positive and negative electrodes of the battery, respectively. The safety device connected to a battery prevents the battery from being damaged or at least from igniting or exploding, even when an external impact caused by pressure, a nail, or a nipper or an external pressure is applied to the battery, by conducting the current of the battery to the safety device and discharging the battery before the battery is damaged by the external impact or external pressure.

Description

本発明は、所定の圧力以上の圧力が加えられるときに電気回路が形成され、電池の充電状態を放電状態に切り換えられる電池用安全素子、及び該安全素子を備えた電池に係る。   The present invention relates to a battery safety element in which an electric circuit is formed when a pressure equal to or higher than a predetermined pressure is applied, and the battery is switched from a charged state to a discharged state, and a battery including the safety element.

近年、電子機器の無線化及びポータブル化が急速に進むにつれて、これらの駆動用電源として高容量及び高エネルギー密度を有する非水電解質二次電池の実用化が進められつつある。しかし、この種の非水電解質二次電池は、外部からの強い圧力や釘、ニッパーなどにより外部から衝撃が加えられる場合、セル内部が損傷され、セルが発火したり爆発したりするといった危険性がある。   In recent years, as electronic devices are rapidly becoming wireless and portable, non-aqueous electrolyte secondary batteries having high capacity and high energy density are being put to practical use as power sources for driving these devices. However, this type of non-aqueous electrolyte secondary battery has a risk that the inside of the cell may be damaged and the cell may ignite or explode if an external impact is applied due to strong external pressure, nails, nippers, etc. There is.

特に、正極活物質は、電圧に敏感であるため、電池が充電され電圧が高ければ高いほど正極と電解液との反応性が強く、この結果、正極表面の分解、電解液の酸化反応が起こり、発火または爆発の危険性が大きくなる。   In particular, since the positive electrode active material is sensitive to voltage, the higher the battery is charged and the higher the voltage, the stronger is the reactivity between the positive electrode and the electrolyte, resulting in decomposition of the positive electrode surface and oxidation of the electrolyte. Increased risk of fire or explosion.

このような安全性の問題は、電池、特に非水電解質二次電池、例えばリチウム二次電池が高容量化しながらエネルギー密度が増大するにつれその重要性は益々高まっている。   Such a safety problem becomes more and more important as the energy density of a battery, particularly a non-aqueous electrolyte secondary battery, such as a lithium secondary battery, increases while increasing its capacity.

本発明は、前記の問題点を解決するためになされたものであって、その目的は、圧力、釘、ニッパーなどによる外部からの衝撃が加えられるときにおける電池の安全性を保障すべく、セルの外部または内部に安全素子を構成し、外部からの衝撃によりセルが損傷される前にセルの充電状態を下げる方法を提供することにある。   The present invention has been made to solve the above-mentioned problems, and its purpose is to ensure the safety of the battery when an external impact is applied by pressure, nails, nippers, etc. It is an object of the present invention to provide a method for reducing the state of charge of a cell before the cell is damaged by an external shock by configuring a safety element outside or inside the cell.

前記目的を達成するために、本発明は、安全素子を備える電池であって、前記安全素子は、所定の圧力以上の圧力が加えられるときに電気回路が形成され、電池の充電状態を放電状態に切り換えることを特徴とする電池を提供する。   In order to achieve the above object, the present invention provides a battery including a safety element, wherein the safety element is formed with an electric circuit when a pressure equal to or higher than a predetermined pressure is applied, and the charged state of the battery is discharged. A battery characterized by switching to is provided.

また、本発明は、所定の圧力以上の圧力が加えられるときに電気回路が形成され、電池の充電状態を放電状態に切り換えられる電池用安全素子を提供する。   The present invention also provides a battery safety element in which an electric circuit is formed when a pressure equal to or higher than a predetermined pressure is applied, and the charge state of the battery can be switched to the discharge state.

さらに、本発明は、圧力により電池が損傷される前に、圧力により安全素子に形成された回路を介して電池の充電状態を放電状態に切り換えることにより電池の安全性を調節する方法を提供する。   Furthermore, the present invention provides a method for adjusting the safety of a battery by switching the charge state of the battery to a discharge state via a circuit formed in the safety element by the pressure before the battery is damaged by the pressure. .

好適な前記安全素子は、第1の金属板と、第2の金属板、及び前記両金属板で挟み込まれ所定の圧力以上の圧力が加えられるときに通電性を発揮するフィルムとを備えてなり、前記第1の金属板は電池の正極に電気的に接続され、第2の金属板は負極に電気的に接続されることである。   The preferred safety element includes a first metal plate, a second metal plate, and a film that is sandwiched between the two metal plates and exhibits electrical conductivity when a pressure higher than a predetermined pressure is applied. The first metal plate is electrically connected to the positive electrode of the battery, and the second metal plate is electrically connected to the negative electrode.

発明の効果
本発明の安全素子を備える電池によれば、圧力、釘、ニッパーなどによる外部からの衝撃または圧力が加えられる場合にも、圧力によりセルが損傷される前にセルの電流を安全素子に通電させ電池を放電させることにより、セルが損傷されることを抑えるか、少なくともセルが発火或いは爆発する現象が起こることを防止することができる。
Advantageous Effects of Invention According to a battery including a safety element of the present invention, even when an external impact or pressure is applied by pressure, a nail, a nipper or the like, the current of the cell is reduced before the cell is damaged by pressure. By energizing the battery and discharging the battery, it is possible to prevent the cell from being damaged, or at least to prevent a phenomenon that the cell ignites or explodes.

従来では、電池の安全性の問題のため非水電解質二次電池、例えばリチウム二次電池においてエネルギー密度を増大させることに制限があったが、本発明の安全素子を備えれば、電池の安全性が確保されると共に作動充電電圧を上昇させることができるため、高エネルギー密度の電池を実現することができる。   Conventionally, there has been a limit to increasing the energy density in a non-aqueous electrolyte secondary battery, such as a lithium secondary battery, due to battery safety problems. However, if the safety element of the present invention is provided, the safety of the battery Therefore, the operating charging voltage can be increased and a battery with a high energy density can be realized.

以下、本発明に係る電池用安全素子及びこれを備えた電池の好適な実施の形態について、添付の図面に基づいて詳細に説明する。   Hereinafter, preferred embodiments of a battery safety element and a battery including the same according to the present invention will be described in detail with reference to the accompanying drawings.

本発明は、圧力、釘、ニッパーなどによる外部からの衝撃または圧力が電池に加えられる場合、これを検知してセルの充電状態を下げる方法として、外部からの衝撃または圧力が加えられるときに通電性を発揮する安全素子を電池に備えることを特徴とする。   In the present invention, when external impact or pressure due to pressure, nails, nippers, or the like is applied to the battery, it is detected as a method to lower the state of charge of the cell. The battery is provided with a safety element that exhibits high performance.

本発明は、外部から衝撃または圧力が加えられるときに通電性を発揮する安全素子の非制限的な例として、所定以上の圧力が発生する場合に圧力の方向に電流を通電させる性質を有するフィルムを電流が流れ得る2枚の金属板(例えば、集電体)で挟み込んでなる安全素子を提供する(図1参照)。   The present invention is a non-limiting example of a safety element that exhibits electrical conductivity when an impact or pressure is applied from the outside, and a film having a property of conducting an electric current in the direction of pressure when a pressure exceeding a predetermined level is generated. Is provided between two metal plates (for example, current collectors) through which a current can flow (see FIG. 1).

このとき、所定以上の圧力が発生する場合に電流を通電させる性質を有するフィルム(PSCF:Pressure Sensitive Conducting Film)の非制限的な例として、異方性導電フィルム(Anisotropic Conductive Film;ACF)などが挙げられる。   At this time, as a non-limiting example of a film (PSCF: Pressure Sensitive Conducting Film) having a property of passing an electric current when a predetermined pressure or more is generated, an anisotropic conductive film (ACF) or the like is used. Can be mentioned.

ACFとは、厚さ15〜35μmの絶縁接着剤に粒径3〜15μmを有する微細な伝導性粒子からなる導電ボールが分散されてなる粘着フィルムをいう。このとき、ACFを構成する粘着フィルムの厚さ及び伝導性粒子の粒径の大きさによって本発明の思想が限定されることではない。前記伝導性粒子としては、各種があるが、炭素ファイバや金属(Ni、Solder)及び金属(Ni/Au)−被覆されたプラスチックボールなどが挙げられる。これは、本発明の実施例において提示した通りに圧力を加え通電を生じさせるPSCFを通称することではない。本発明で説明したように圧力を加えて通電を生じさせるフィルムであればいずれも本発明の原理に適用できることが当該分野における通常の知識を有する者であれば分かる。   ACF refers to an adhesive film in which conductive balls made of fine conductive particles having a particle size of 3 to 15 μm are dispersed in an insulating adhesive having a thickness of 15 to 35 μm. At this time, the idea of the present invention is not limited by the thickness of the pressure-sensitive adhesive film constituting the ACF and the size of the conductive particles. Examples of the conductive particles include carbon fibers, metal (Ni, Solder), and metal (Ni / Au) -coated plastic balls. This is not to refer to the PSCF that applies pressure and causes energization as presented in the embodiments of the present invention. As described in the present invention, those having ordinary knowledge in the field can understand that any film that applies current by applying pressure can be applied to the principle of the present invention.

粘着物質の種類としては、熱可塑性物質(スチレンブタジエンゴム、ポリビニルブチレン)、熱硬化性物質(エポキシ樹脂、ポリウレタン、アクリル樹脂)、及び熱可塑性物質と熱硬化性物質との混合物質が挙げられる。   Examples of the adhesive material include thermoplastic materials (styrene butadiene rubber, polyvinyl butylene), thermosetting materials (epoxy resin, polyurethane, acrylic resin), and mixed materials of thermoplastic materials and thermosetting materials.

一方、本発明において使用可能な金属板の材料としては、電気伝導性を有するものであればいずれも使用可能である。例えば、アルミニウム金属、銅金属、ニッケル金属などがある。   On the other hand, as the metal plate material that can be used in the present invention, any material having electrical conductivity can be used. For example, there are aluminum metal, copper metal, nickel metal, and the like.

前記金属板は、熱伝導性にも優れていればよく、これにより平常時または特殊な状況でも電池内部の熱が端子を介して熱伝導性の金属板に伝わって分散できる。   The metal plate only needs to be excellent in thermal conductivity, so that the heat inside the battery can be transferred to the thermally conductive metal plate via the terminal and can be dispersed even in normal or special circumstances.

以下、本発明により外部から衝撃または圧力が加えられるとき、所定以上の圧力が加えられれば通電性を発揮する安全素子を備えた電池の作用機転を、図面を参照して説明することにする。   Hereinafter, when a shock or pressure is applied from the outside according to the present invention, a working mechanism of a battery provided with a safety element that exhibits electrical conductivity when a predetermined pressure or more is applied will be described with reference to the drawings.

本発明の安全素子は、第1の金属板と、第2の金属体、及び前記両金属板で挟み込まれ所定の圧力以上の圧力が加えられるときに通電性を発揮するフィルムとを備えてなり、当該安全素子の一例として、図1では集電体が前記金属板の役割を果たし、ACFが前記通電性を発揮するフィルムの役割を果たす。   The safety element of the present invention comprises a first metal plate, a second metal body, and a film that exhibits electrical conductivity when a pressure higher than a predetermined pressure is applied between the two metal plates. As an example of the safety element, in FIG. 1, the current collector serves as the metal plate, and the ACF serves as a film that exhibits the electrical conductivity.

ACFは、平常時には電流が通電しない不導体として働き、所定以上の圧力が発生すれば圧力の方向に電流を通電させる性質をもつ。   The ACF functions as a non-conductor that does not pass current in normal times, and has a property of passing current in the direction of pressure when a pressure exceeding a predetermined level is generated.

図1に示すように、ACFの両面に配される二枚の金属板のうち第1の金属板(集電体)は、電池の正極に電気的に接続されており、第2の金属板(集電体)は、電池の負極に電気的に接続されている。   As shown in FIG. 1, the first metal plate (current collector) of the two metal plates arranged on both sides of the ACF is electrically connected to the positive electrode of the battery, and the second metal plate The (current collector) is electrically connected to the negative electrode of the battery.

このとき、本発明の安全素子が接続された電池は、前記金属板に外部から圧力が加えられていないときは前記二枚の金属板がACFにより電気的に絶縁されているため、二枚の金属板の間を電流が流れることなく、電池は正常作動し充電状態を保持する。   At this time, in the battery to which the safety element of the present invention is connected, the two metal plates are electrically insulated by ACF when no pressure is applied to the metal plate from the outside. The battery operates normally and maintains a charged state without current flowing between the metal plates.

一方、本発明の安全素子が接続された電池に外部からの衝撃などにより圧力が加えられるとき、その圧力が所定の圧力以上になれば、ACFが通電させる性質を発揮するため、前記二枚の金属板は、ACFを介して電気的に接続され電池を放電させることで電池内部の電圧を急降下させる。放電状態の電池は、外部からの圧力、釘、ニッパーなどによる衝撃を受ける場合にも発火或いは爆発することがない。従って、本発明は、圧力、釘、ニッパーなどによる外部からの衝撃により所定の圧力以上が金属板に加えられれば、セルが爆発する前にセルの充電状態を下げ、電池の安全性を向上することができる。   On the other hand, when pressure is applied to the battery to which the safety element of the present invention is connected by an external impact or the like, if the pressure exceeds a predetermined pressure, the ACF exhibits the property of energizing. The metal plate is electrically connected via the ACF, and discharges the battery to rapidly drop the voltage inside the battery. A discharged battery does not ignite or explode even when subjected to an external pressure, impact by a nail, nipper or the like. Therefore, the present invention improves the safety of the battery by reducing the state of charge of the cell before the cell explodes if a pressure exceeding a predetermined pressure is applied to the metal plate due to external impact such as pressure, nails, nippers, etc. be able to.

本発明の安全素子は、外部からの衝撃または圧力が加えられるときにおける主に電池に働く圧力の方向に直交するように設けられることが好ましい。   The safety element of the present invention is preferably provided so as to be orthogonal to the direction of pressure mainly acting on the battery when an external impact or pressure is applied.

また、本発明の安全素子は、セルの外部または内部に設けてもよいが、外部に設けることが好ましい。   The safety element of the present invention may be provided outside or inside the cell, but is preferably provided outside.

電池の外部に設けられた本発明の安全素子は、露出された状態で使用してもよく、また、電気的に絶縁性を有する高分子層で被覆して使用してもよい。   The safety element of the present invention provided outside the battery may be used in an exposed state, or may be used by being coated with an electrically insulating polymer layer.

一方、図2に本発明の安全素子を電池に接続した状態を具体的に示している。   On the other hand, the state which connected the safety element of this invention to the battery in FIG. 2 is shown concretely.

図2は、ポーチ形電池に本発明の安全素子を接続したことを示している。   FIG. 2 shows that the safety element of the present invention is connected to a pouch-type battery.

一般に、ポーチ形電池は、積層型であって、一枚以上の正極板、及び前記正極板と交互に積層された一枚以上の負極板とを備えている。このとき、積層型電池は、一枚以上の正極板を接続しこれを電池の外部に接続する正極リードと、一枚以上の負極板を接続し電池の外部に接続する負極リードとが電池包装材の外部の電源に接続される構造となっている。   In general, the pouch-type battery is of a stacked type, and includes one or more positive electrode plates and one or more negative electrode plates alternately stacked with the positive electrode plates. At this time, in the stacked battery, a positive electrode lead that connects one or more positive plates and connects them to the outside of the battery, and a negative electrode lead that connects one or more negative plates and connects to the outside of the battery is a battery package. It is structured to be connected to a power source outside the material.

このとき、第1の金属板と、第2の金属板、及び前記両金属板で挟み込まれたACFとから構成された本発明の安全素子は、前記最外郭の正極板及び/または最外郭の負極板に共に積層されている。このとき、第1の金属板は、正極板の一部または正極リードまたは正極端子に電気的に接続されており、第2の金属板は、負極板の一部または負極リードまたは負極端子に電気的に接続されている。   At this time, the safety element of the present invention composed of the first metal plate, the second metal plate, and the ACF sandwiched between the two metal plates has the outermost positive plate and / or the outermost plate. It is laminated together on the negative electrode plate. At this time, the first metal plate is electrically connected to a part of the positive electrode plate or the positive electrode lead or the positive electrode terminal, and the second metal plate is electrically connected to a part of the negative electrode plate or the negative electrode lead or the negative electrode terminal. Connected.

このとき、本発明の安全素子は、電極の極板に直接隣接して積層してもよいが、電池包装材の外部に積層することで電気的にのみ正極、負極に接続することが好ましい。   At this time, the safety element of the present invention may be laminated directly adjacent to the electrode plate of the electrode, but it is preferable that the safety element is electrically connected only to the positive electrode and the negative electrode by being laminated outside the battery packaging material.

図3は、缶形電池に本発明の安全素子を接続したことを示している。   FIG. 3 shows that the safety element of the present invention is connected to a can-type battery.

一般に、缶形電池は、正極板と、負極板、及びセパレータ膜とからなる電極組立体を缶とキャップとからなる容器内に備えてなるものであり、前記容器は、一方の電極の電極端子の役割を果たし(図3では、正極端子の役割)、逆の電極の電極端子(図3では負極端子)が絶縁された状態で前記容器から突出している。   In general, a can-type battery includes an electrode assembly including a positive electrode plate, a negative electrode plate, and a separator film in a container including a can and a cap, and the container includes an electrode terminal of one electrode. The electrode terminal of the opposite electrode (the negative electrode terminal in FIG. 3) protrudes from the container in an insulated state.

このとき、缶形電池の容器は、前記本発明の安全素子のうち第1の金属板の役割を果たすことができる。従って、本発明の安全素子の第2の金属板は、前記容器の少なくとも一面と平行に設けられ、その間にACFが介在し、前記第2の金属板の一部が前記逆の電極の電極端子に電気的に接続されている。   At this time, the container of the can battery can serve as the first metal plate in the safety element of the present invention. Therefore, the second metal plate of the safety element of the present invention is provided in parallel with at least one surface of the container, the ACF is interposed therebetween, and a part of the second metal plate is an electrode terminal of the reverse electrode. Is electrically connected.

一方、本発明の安全素子が適用可能な電池としては、充電されている電池であればいずれでもよく、一次電池、二次電池のいずれも可能である。非制限的な例として、a)リチウムイオンを吸蔵・放出可能な正極と;b)リチウムイオンを吸蔵・放出可能な負極と;c)多孔性セパレータ膜;及びd)リチウム塩と電解液化合物を含む非水電解液とを含むリチウム二次電池が挙げられる。   On the other hand, the battery to which the safety element of the present invention can be applied may be any battery as long as it is charged, and either a primary battery or a secondary battery is possible. Non-limiting examples include: a) a positive electrode capable of inserting and extracting lithium ions; b) a negative electrode capable of inserting and extracting lithium ions; c) a porous separator film; and d) a lithium salt and an electrolyte compound. And a lithium secondary battery containing the nonaqueous electrolyte solution.

前記非水電解液は、環状カーボネート及び/または線状カーボネートを含む。前記環状カーボネートの例を挙げれば、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、γ−ブチロラクトン(GBL)などがある。前記線状カーボネートの例を挙げれば、ジエチルカーボネート(DEC)、ジメチルカーボネート(DMC)、エチルメチルカーボネート(EMC)及びメチルプロピルカーボネート(MPC)からなる群より選ばれた少なくとも1種であることが好ましい。   The non-aqueous electrolyte contains a cyclic carbonate and / or a linear carbonate. Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), and γ-butyrolactone (GBL). Examples of the linear carbonate are preferably at least one selected from the group consisting of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and methyl propyl carbonate (MPC). .

前記非水電解液に含まれるリチウム塩は、LiClO、LiCFSO、LiPF、LiBF、LiAsF、及びLiN(CFSOからなる群より選ばれることが好ましい。 The lithium salt contained in the non-aqueous electrolyte is preferably selected from the group consisting of LiClO 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , LiAsF 6 , and LiN (CF 3 SO 2 ) 2 .

前記負極活物質としては、炭素、リチウム金属またはその合金を使用することが好ましい。その他、リチウムが吸蔵・放出でき、リチウムに対する電位が2V未満であるTiO、SnOのような金属酸化物も使用可能である。 As the negative electrode active material, it is preferable to use carbon, lithium metal, or an alloy thereof. In addition, metal oxides such as TiO 2 and SnO 2 that can occlude and release lithium and have a potential with respect to lithium of less than 2 V can be used.

前記正極活物質としては、リチウム含有遷移金属酸化物が好ましく、例えば、LiCoO、LiNiO、LiMn、LiMnO、及びLiNi1−XCo(ここで、0<X<1)からなる群より選ばれた少なくとも1種であることが好ましい。MnOのような金属酸化物或いはこれらの混合物からなる正極でもよい。 The positive electrode active material is preferably a lithium-containing transition metal oxide. For example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , and LiNi 1-X Co X O 2 (where 0 <X <1 And at least one selected from the group consisting of: A positive electrode made of a metal oxide such as MnO 2 or a mixture thereof may be used.

また、前記多孔性セパレータ膜の例として、ポリオレフィン系多孔性セパレータ膜が挙げられる。   Examples of the porous separator membrane include polyolefin-based porous separator membranes.

本発明のリチウム二次電池は、通常の方法で負極と正極とで多孔性セパレータ膜を挟み込み、前記したLiPFなどのリチウム塩と添加剤を含む非水電解液を投入して製造することができる。 The lithium secondary battery of the present invention can be manufactured by inserting a non-aqueous electrolyte containing a lithium salt such as LiPF 6 and an additive as described above, with a porous separator film sandwiched between a negative electrode and a positive electrode by a normal method. it can.

以下、実施例に基づいて本発明をより詳細に説明する。なお、実施例は、本発明を例示するためのものに過ぎなく、本発明を限定するものではない。   Hereinafter, the present invention will be described in more detail based on examples. In addition, an Example is only for demonstrating this invention and does not limit this invention.

実施例1
図2に示すように、第1の金属板(正極集電体)と、第2の金属板(負極集電体)、及び前記両金属板で挟み込まれたACFとからなる本発明の安全素子を、ポーチ形態で製造された電池(cell)に、第1の金属板が正極に電気的に接続され、第2の金属板が負極に電気的に接続されるように取り付けた。使用したポーチ形電池における正極にはLiCoOが、負極にはカーボンが使用され、電解液としてはEC:EMC(1:2)ベース組成を有する1MのLiPF溶液を使用した。
Example 1
As shown in FIG. 2, the safety element of the present invention comprises a first metal plate (positive electrode current collector), a second metal plate (negative electrode current collector), and an ACF sandwiched between the two metal plates. Was attached to a cell manufactured in a pouch form such that the first metal plate was electrically connected to the positive electrode and the second metal plate was electrically connected to the negative electrode. In the pouch-type battery used, LiCoO 2 was used for the positive electrode, carbon was used for the negative electrode, and a 1M LiPF 6 solution having an EC: EMC (1: 2) base composition was used as the electrolyte.

前記電池を4.2Vに充電し、直径1cmの棒で3mm/分の速度で本発明の安全素子に対し垂直方向に押圧してローカル・クラッシュ実験を行った。   The battery was charged to 4.2 V, and a local crash experiment was conducted by pressing the battery in a vertical direction against the safety element of the present invention at a speed of 3 mm / min with a 1 cm diameter rod.

前記実験の結果、ACFに加えられる圧力が上昇するに伴って電圧が0V近くまで急降下し、セルの爆発は起こらず安定し、発熱温度は約70℃以下と非常に低かった(図4参照)。   As a result of the experiment, as the pressure applied to the ACF increased, the voltage suddenly dropped to near 0V, the cell did not explode and was stable, and the exothermic temperature was very low at about 70 ° C. or less (see FIG. 4). .

実施例2
実施例1より悪条件下で実験するために電池を4.3Vまで充電したことを除き、実施例1と同じ方法で電池の製造及びローカル・クラッシュ実験を行った。
Example 2
A battery was manufactured and a local crash experiment was performed in the same manner as in Example 1 except that the battery was charged to 4.3 V in order to conduct an experiment under worse conditions than in Example 1.

前記実験の結果、圧力が上昇するに伴って電圧が0V近くまで急降下し、セルの爆発は起こらず安定し、発熱温度も約70℃以下と非常に低かった(図5参照)。   As a result of the experiment, as the pressure increased, the voltage dropped rapidly to near 0 V, the cell did not explode and was stable, and the heat generation temperature was very low at about 70 ° C. or less (see FIG. 5).

実施例3
実施例2より悪条件下で実験するために電池を4.4Vまで充電したことを除き、実施例1と同じ方法で電池の製造及びローカル・クラッシュ実験を行った。
Example 3
A battery was manufactured and a local crash experiment was performed in the same manner as in Example 1 except that the battery was charged to 4.4 V in order to perform an experiment under worse conditions than in Example 2.

前記実験の結果、圧力が上昇するに伴って電圧が0V近くまで急降下し、セルの爆発は起こらず安定し、発熱温度も約70℃以下と非常に低かった(図6参照)。   As a result of the experiment, as the pressure increased, the voltage dropped rapidly to near 0 V, the cell did not explode and was stable, and the exothermic temperature was very low at about 70 ° C. or less (see FIG. 6).

比較例1
本発明の安全素子を取り付けなかったことを除き、実施例1と同じ方法で電池の製造及びローカル・クラッシュ実験を行った。
Comparative Example 1
A battery was manufactured and a local crash experiment was performed in the same manner as in Example 1 except that the safety element of the present invention was not attached.

前記実験の結果、セルの爆発が起こり、爆発の前に電圧の降下は起こらず、爆発と同時に電圧の降下及び発熱が起こった。発熱温度も約600℃以上と非常に高かった(図7参照)。   As a result of the experiment, a cell explosion occurred, no voltage drop occurred before the explosion, and a voltage drop and heat generation occurred simultaneously with the explosion. The exothermic temperature was also very high at about 600 ° C. or higher (see FIG. 7).

本発明に係るACF安全素子の作動原理を示す模式図である。It is a schematic diagram which shows the working principle of the ACF safety element which concerns on this invention. 本発明に係るACF安全素子が電気的に接続されたポーチ形電池を示す模式図である。It is a schematic diagram which shows the pouch-type battery to which the ACF safety element which concerns on this invention was electrically connected. 本発明に係るACF安全素子が電気的に接続された金属缶形電池を示す模式図である。It is a schematic diagram which shows the metal can-type battery to which the ACF safety element which concerns on this invention was electrically connected. 実施例1で作製された電池のローカル・クラッシュ実験結果を示すグラフである。4 is a graph showing the results of local crash experiments for the battery manufactured in Example 1. FIG. 実施例2で作製された電池のローカル・クラッシュ実験結果を示すグラフである。6 is a graph showing the results of a local crash experiment for a battery manufactured in Example 2. 実施例3で作製された電池のローカル・クラッシュ実験結果を示すグラフである。6 is a graph showing the results of a local crash experiment of a battery manufactured in Example 3. 比較例1で作製された電池のローカル・クラッシュ実験結果を示すグラフである。6 is a graph showing the results of a local crash experiment of a battery manufactured in Comparative Example 1.

Claims (11)

安全素子を備える電池であって、
前記安全素子が、所定の圧力以上の圧力が加えられるときに電気回路が形成され、電池の充電状態を放電状態に切り換えることを特徴とする、電池。
A battery comprising a safety element,
The battery is characterized in that an electric circuit is formed when a pressure equal to or higher than a predetermined pressure is applied to the safety element, and the battery is switched from a charged state to a discharged state.
前記安全素子が、第1の金属板と、第2の金属板、及び前記両金属板で挟み込まれ所定の圧力以上の圧力が加えられるときに通電性を発揮するフィルム(PSCF)とを備えてなり、前記第1の金属板は正極に電気的に接続され、第2の金属板は負極に電気的に接続されることを特徴とする、請求項1に記載の電池。   The safety element includes a first metal plate, a second metal plate, and a film (PSCF) that is sandwiched between the two metal plates and exhibits electrical conductivity when a pressure higher than a predetermined pressure is applied. The battery according to claim 1, wherein the first metal plate is electrically connected to the positive electrode, and the second metal plate is electrically connected to the negative electrode. 前記フィルムが、異方性導電フィルム(ACF)であることを特徴とする、請求項2に記載の電池。   The battery according to claim 2, wherein the film is an anisotropic conductive film (ACF). 前記安全素子が、外部から衝撃が加えられるときにおける主に電池に働く圧力の方向に直交するように設けられることを特徴とする、請求項1に記載の電池。   The battery according to claim 1, wherein the safety element is provided so as to be orthogonal to a direction of pressure mainly acting on the battery when an impact is applied from the outside. 前記電池が、リチウム二次電池であることを特徴とする、請求項1に記載の電池。   The battery according to claim 1, wherein the battery is a lithium secondary battery. 所定の圧力以上の圧力が加えられるときに電気回路が形成され、電池の充電状態を放電状態に切り換えられることを特徴とする、電池用安全素子。   A safety element for a battery, wherein an electric circuit is formed when a pressure equal to or higher than a predetermined pressure is applied, and the charge state of the battery is switched to a discharge state. 第1の金属板と、第2の金属板、及び前記両金属板で挟み込まれ所定の圧力以上の圧力が加えられるときに通電性を発揮するフィルムとを備えてなる電池用安全素子であって、
前記第1の金属板は電池の正極に電気的に接続され、第2の金属板は負極に電気的に接続されることを特徴とする、請求項6に記載の電池用安全素子。
A safety element for a battery comprising a first metal plate, a second metal plate, and a film that is sandwiched between the two metal plates and exhibits electrical conductivity when a pressure equal to or higher than a predetermined pressure is applied. ,
The battery safety element according to claim 6, wherein the first metal plate is electrically connected to a positive electrode of the battery, and the second metal plate is electrically connected to a negative electrode.
前記フィルムが、異方性導電フィルム(ACF)であることを特徴とする、請求項7に記載の安全素子。   The safety element according to claim 7, wherein the film is an anisotropic conductive film (ACF). 前記金属板が、熱伝導性を有することを特徴とする、請求項7に記載の安全素子。   The safety element according to claim 7, wherein the metal plate has thermal conductivity. 圧力により電池が損傷される前に、圧力により安全素子に形成された電気回路を介して電池の充電状態を放電状態に切り換えることにより電池の安全性を調節する方法。   A method of adjusting the safety of a battery by switching the state of charge of the battery to a discharged state via an electrical circuit formed in the safety element by pressure before the battery is damaged by pressure. 前記安全素子が、第1の金属板と、第2の金属板、及び前記両金属板で挟み込まれ所定の圧力以上の圧力が加えられるときに通電性を発揮するフィルムとを備えてなり、前記第1の金属板は電池の正極に電気的に接続され、第2の金属板は負極に電気的に接続されることを特徴とする、請求項10に記載の電池の安全性を調節する方法 。   The safety element comprises a first metal plate, a second metal plate, and a film that exhibits conductivity when sandwiched between the two metal plates and a pressure equal to or higher than a predetermined pressure is applied, 11. The method of adjusting the safety of a battery according to claim 10, wherein the first metal plate is electrically connected to the positive electrode of the battery, and the second metal plate is electrically connected to the negative electrode. .
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